JPS61291592A - Production of diorganotin oxide - Google Patents
Production of diorganotin oxideInfo
- Publication number
- JPS61291592A JPS61291592A JP60131646A JP13164685A JPS61291592A JP S61291592 A JPS61291592 A JP S61291592A JP 60131646 A JP60131646 A JP 60131646A JP 13164685 A JP13164685 A JP 13164685A JP S61291592 A JPS61291592 A JP S61291592A
- Authority
- JP
- Japan
- Prior art keywords
- diorganotin
- oxide
- organic solvent
- formula
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 150000004820 halides Chemical class 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical group 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LHHPEAQVCCPLBC-UHFFFAOYSA-N tributyltin;hydrate Chemical compound O.CCCC[Sn](CCCC)CCCC LHHPEAQVCCPLBC-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YYCPKPBVZMQMQT-UHFFFAOYSA-L butyl(diiodo)tin Chemical compound CCCC[Sn](I)I YYCPKPBVZMQMQT-UHFFFAOYSA-L 0.000 description 1
- GTVGGZBELVUNIL-UHFFFAOYSA-K butyltin(3+);triiodide Chemical compound CCCC[Sn](I)(I)I GTVGGZBELVUNIL-UHFFFAOYSA-K 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- HLATYLIVBMECMN-UHFFFAOYSA-L dibutyltin(2+);diiodide Chemical compound CCCC[Sn](I)(I)CCCC HLATYLIVBMECMN-UHFFFAOYSA-L 0.000 description 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- UQCWKRIUDXVWRV-UHFFFAOYSA-L diiodo(dioctyl)stannane Chemical compound CCCCCCCC[Sn](I)(I)CCCCCCCC UQCWKRIUDXVWRV-UHFFFAOYSA-L 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- VPPWQRIBARKZNY-UHFFFAOYSA-N oxo(diphenyl)tin Chemical compound C=1C=CC=CC=1[Sn](=O)C1=CC=CC=C1 VPPWQRIBARKZNY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Description
【発明の詳細な説明】 りえ上立旦皿土１ 本発明は、ジオルガノ錫オキサイドの製造法に関する。[Detailed description of the invention] Rie Kami Tatedan Plate 1 The present invention relates to a method for producing diorganotin oxide.
本発明の目的物であるジオルガノ錫オキサイドは、通常
は式Ｒ２Ｓ ｎ Ｏで表わされるが、この物質の組成は
複雑であって、式Ｒ２Ｓ ｎ Ｏで表わされるも（７）
＋７）ほか、例えばＲ２Ｓ ｎ （ＯＨ）２、鎖状オリ
ゴで−として例えば
（式中のｍは１８以下の整数を表わす、）、あるいは環
状オリゴマーとして例えば
などの式で表わされるものの存在も考えられている。本
発明においてジオルガノ錫オキサイドとは、これらのす
べてを含むものである。すなわち、１個の錫原子にＲで
表わされる有機基が２個結合し、且つ酸素がそれ自体で
あるいは一〇Ｈ基または一〇Ｍ基（Ｍはアルカリ金属原
子を表わす、）となって結合している４価の錫の化合物
である。Diorganotin oxide, which is the object of the present invention, is usually represented by the formula R2S n O, but the composition of this substance is complex, and although it is represented by the formula R2S n O (7)
+7) In addition, for example, R2S n (OH)2, linear oligomers represented by - (in the formula, m represents an integer of 18 or less), or cyclic oligomers such as, for example, may also exist. ing. In the present invention, diorganotin oxide includes all of these. That is, two organic groups represented by R are bonded to one tin atom, and oxygen is bonded by itself or as a 10H group or 10M group (M represents an alkali metal atom). It is a compound of tetravalent tin.
ジオルガノ錫オキサイドは、ポリ塩化ビニル樹脂用安定
剤、有機合成触媒などに多量に使用されており、またポ
リエステル重合触媒、硬化性樹脂原料、難燃性材料、酸
化錫膜関係などの新しい用途も実用化されつつある。Diorganotin oxide is used in large quantities as a stabilizer for polyvinyl chloride resin, an organic synthesis catalyst, etc., and new applications such as polyester polymerization catalysts, curable resin raw materials, flame retardant materials, and tin oxide films are also being put into practical use. It is becoming more and more popular.
え１立韮遣
ジオルガノ錫オキサイドは一般式Ｒ２５ｎｘ２で表わさ
れるジオルガノ錫ジハライドの加水分解によってつくら
れる。このジオルガノ錫ジハライドは、それがいわゆる
アルキルアルミニウム法〔「ジャーナル・オブ・オーガ
ニック・ケミストリＪ （Ｊ 、Ｏｒｇ、Ｃｈｅｍ、
）第２５巻、第２２５３ページ（１９６０）、「アンナ
ーレン・デア・ヘミ−Ｊ （Ａｎｎ、）６５３，１５
７（１９６２））またはグリニヤール法〔「プロシーデ
ィング争オブ・ザφケミストリ（Ｐｒｏ−ｃｅｅｄｉｎ
ｇ ｏｆ ｔｈｅ Ｃｈｅｍ、）Ｓ、Ｃ，１９，
２９０（１９０３）、「ジャーナル・オブ命ジ・アメリ
カン・ケミカル・ソサイアティ（Ｊ 、Ａｍ、Ｃｈｅｍ
、Ｓｏｃ、）第７９巻第５８８１ページ（１９５７）、
同誌、第７９巻第５１５ページ（１９５７））でつくら
れたものである場合には、ハロゲンが塩素であるジオル
ガノ錫ジクロライドの形でつくられ、この物質は工業的
な蒸留が可能であるので、反応時に副生ずるモノクロラ
イドあるいはトリクロライドの含有量の低いジクロライ
ドを蒸留によって得ることができ、そのようにして純度
を高められたジオルガノ錫ジクロライドは、例えばアル
コール類を溶媒として容易に加水分解を行なうことがで
きる。E1. Diorganotin oxide is produced by hydrolysis of diorganotin dihalide represented by the general formula R25nx2. This diorganotin dihalide is produced by the so-called alkyl aluminum method [Journal of Organic Chemistry J (J, Org, Chem,
) Vol. 25, p. 2253 (1960), "Annaren der Hemie-J (Ann,) 653, 15
7 (1962)) or the Grignard Act [``Proceedings of the
g of the Chem,)S,C,19,
290 (1903), Journal of the American Chemical Society.
, Soc, ) Volume 79, Page 5881 (1957),
If it is produced in the same magazine, Vol. 79, p. 515 (1957), it is produced in the form of diorganotin dichloride, where the halogen is chlorine, and this substance can be industrially distilled. Dichloride with a low content of monochloride or trichloride produced as a by-product during the reaction can be obtained by distillation, and diorganotin dichloride with increased purity can be easily hydrolyzed using alcohol as a solvent, for example. I can do it.
しかしながらＲＳ ｎ Ｘ ２で表わされるジオルガノ
錫ジハライドが、いわゆるヨード法〔「工業化学雑誌」
第６３巻、第１１４ページ（１９６０）、Ａｐｐｌ、Ｃ
ｈｅｍ、第４巻、第３０１ページ（１９５４）、同誌第
７巻、第３６９ページ（１９５７）、特公昭３５−７８
１０号公報〕でつくられる場合にはＲＳ ｎ Ｘ ２は
ジオルガノ錫ジアイオダイドとして得られ、この物質は
熱分解を受けやすいため工業的な蒸留が困難であって、
副生ずるモノアイオダイドあるいはトリアイオダイドな
どとの分離が困難である。そしてこのような純度の高く
ないジオルガノ錫ジアイオダイドをアルコール類あるい
はケトン類などのような水溶性溶媒中で加水分解すると
、得られる製品の結晶形が極めて細かいため口過が非常
に困難となるか、もしくは顆粒状又は塊状となり、加水
分解を受けずに内部に包含されて残る原料物質の量も多
いという欠点がある。However, the diorganotin dihalide represented by RS n
Volume 63, page 114 (1960), Appl, C
hem, Volume 4, Page 301 (1954), Volume 7, Page 369 (1957), Special Publication 1978-1978
No. 10], RS n
It is difficult to separate it from by-products such as mono-iodide or tri-iodide. When such low-purity diorganotin diaiodides are hydrolyzed in water-soluble solvents such as alcohols or ketones, the crystalline form of the resulting product is extremely fine, making it extremely difficult to pass through the mouth. Otherwise, it becomes granular or lumpy, and there is a drawback that a large amount of the raw material remains contained inside without being hydrolyzed.
またベンゼン、トルエンあるいはキシレンなどのような
疎水性芳香族炭化水素系溶媒中で加水分解を行なう方法
もあるが、この場合には生成物がゲル状になるような傾
向が見られるので口過性が悪いばかりでなく、これらの
溶媒は可燃性であるため常に引火、爆発などの危険があ
る。そのほかに有機溶媒を使用しないでアルカリ水溶液
だけで加水分解を行なった場合には、口過しやすい粉末
状製品が得られにくく、且つ加水分解反応が順調に進行
しにくいため、製品中に多量の未反応物が残存するとい
う欠点がある。There is also a method of performing hydrolysis in a hydrophobic aromatic hydrocarbon solvent such as benzene, toluene, or xylene, but in this case, the product tends to be gel-like, resulting in poor oral hygiene. Not only is this bad, but these solvents are flammable, so there is always a risk of fire or explosion. In addition, if hydrolysis is carried out using only an alkaline aqueous solution without using an organic solvent, it is difficult to obtain a powdered product that is easy to swallow, and the hydrolysis reaction is difficult to proceed smoothly, resulting in a large amount of product being contained in the product. There is a drawback that unreacted substances remain.
発明が解決しようとする問題点
本発明の目的は、下記（１）〜（３）のすべてを満たす
ジオルガノ錫オキサイドの製造方法を提供することであ
る。Problems to be Solved by the Invention An object of the present invention is to provide a method for producing diorganotin oxide that satisfies all of the following (1) to (3).
（１）Ｒ３ｎＸ で表わされる錫化合物（これはｐ
ｑ
ＲＳ ｎ Ｘ ２で表わされるジオルガノ錫ジハライド
の製造に際して副生ずる。）を含有するＲ Ｓ ｎ
Ｘ ２を原料として使用して、未反応へ０ゲン化物を含
有せず、且つ原料中に併存する各種ハライドから生成す
るオキサイドをも含有しないジオルガノ錫オキサイドを
製造する方法を提供すること。(1) Tin compound represented by R3nX (this is p
It is produced as a by-product during the production of diorganotin dihalide represented by q RS n X 2. ) containing R S n
To provide a method for producing diorganotin oxide which does not contain unreacted 0-genides and does not contain oxides generated from various halides coexisting in the raw material, using X2 as a raw material.
（２）口過性の良好な粉末状のジオルガノ錫オキサイド
を製造する方法を提供すること。(2) To provide a method for producing a powdered diorganotin oxide with good oral properties.
（３）引火、爆発などの危険なくジオルガノ錫オキサイ
ドを製造する方法を提供すること。(3) To provide a method for producing diorganotin oxide without risks such as ignition and explosion.
問題点 決 るための手
本発明は、一般式 Ｒ２Ｓ ｎ Ｘ ２（式中のＲは炭
素原子数が１ないし８個のアルキル基、フェニル基また
はシクロヘキシル基を表わし、Ｘはハロゲン原子を表わ
す、）
で表わされるジオルガノ錫ジハライドまたは一般式 Ｒ
５ｎＸ２で表わされるジオルガノ錫ジハライドと
一般式 ＲＳ ｎ Ｘ ｑ
（式中のＲ及び又は上記と同じ意義を有し、ｐ及びｑは
それぞれ０、ｌ、３または４を表わし、しかもＰとｑと
の和は４である。）
で表わされるオルガノ錫ハライドとの混合物を、塩素系
有機溶媒中において、アルカリ金属水酸化物または水酸
化アンモニウムの水溶液によって加水分解することを特
徴とするジオルガノ錫オキサイドの製造法である。Problems to be Solved The present invention is based on the general formula R2S n ) Diorganotin dihalide or general formula R
Diorganotin dihalide represented by 5nX2 and the general formula RS n Production of diorganotin oxide, characterized in that a mixture with an organotin halide represented by It is the law.
本発明の構成要素について、以下に詳説する。The components of the present invention will be explained in detail below.
（塩素系有機溶媒）
本発明に使用する塩素系有機溶媒としては、例えば１，
１．１−）リクロロエタン、トリクロロエチレン、パー
クロロエチレン、クロロホルム、四塩化炭素、塩化ブチ
ル、１，２−ジクロロプロパン、モノクロロベンゼンあ
るいはジクロロベンゼンなどを挙げることができるが、
これらのみに限られるものではない。(Chlorinated organic solvent) Examples of the chlorinated organic solvent used in the present invention include 1,
1.1-) Lichloroethane, trichlorethylene, perchloroethylene, chloroform, carbon tetrachloride, butyl chloride, 1,2-dichloropropane, monochlorobenzene or dichlorobenzene, etc. can be mentioned,
It is not limited to these only.
これらの塩素系有機溶媒の使用量は、反応に用いるオル
ガノ錫ハライド１重量部に対して工ないし１０重量部と
することができ、好ましい範囲は１〜５重量部である。The amount of these chlorinated organic solvents to be used can be from 1 to 10 parts by weight per 1 part by weight of the organotin halide used in the reaction, and the preferred range is from 1 to 5 parts by weight.
（アルカリ水溶液）
加水分解に使用するアルカリ金属水酸化物または水酸化
アンモニウムの水溶液の濃度は３１０な゛いし２０重量
％が適当であり、その使用量は加水分解に必要どされる
計算量のやや過剰量から２倍量の範囲内で選択され、さ
らに大過剰を使用することは無意味である。(Aqueous alkaline solution) The appropriate concentration of the aqueous solution of alkali metal hydroxide or ammonium hydroxide used for hydrolysis is 310 to 20% by weight, and the amount used is slightly smaller than the amount of calculation required for hydrolysis. It is selected within the range of two times the excess amount, and it is pointless to use even larger excesses.
ここで使用するアルカリ金属水酸化物としては水酸化ナ
トリウムおよび水酸化カリウムが経済的に使用され、と
くに前者が安価であって好ましい。As the alkali metal hydroxide used here, sodium hydroxide and potassium hydroxide are economically used, and the former is particularly preferred because it is inexpensive.
（ジオルガノ錫オギサイドの分離）
ジオルガノ錫オキサイドは塩素系有機溶媒にも上記のア
ルカリ性水溶液にも溶解しないが。(Separation of diorganotin oxide) Diorganotin oxide does not dissolve in either the chlorinated organic solvent or the above alkaline aqueous solution.
ＲＳ ｎ Ｘ ２及びＲ、Ｓ ｎ Ｘ 、はいずれも塩
素系有機溶媒によく溶解し、またＲ Ｓ ｎ Ｘ ３の
加水分解によって生成するＲ３ ｎ （ＯＨ） ３及び
ＲＳ ｎ （ＯＭ ） ３は上記のアルカリ性水溶液に
溶解し、Ｒ３Ｓ ｎ Ｘの加水分解によって生成する（
ＲＳ ｎ） ２０は塩素系有機溶媒に良く溶解するので
、目的物と未反応物及び各種副生物との分離は容易に行
なわれる。RS n X 2 and R, S n It is dissolved in an alkaline aqueous solution of and produced by hydrolysis of R3S n
Since RS n) 20 dissolves well in chlorinated organic solvents, separation of the target product from unreacted products and various by-products can be easily performed.
（操作の概説） 本発明の方法は、例えば次のようにして行なわれる。(Overview of operations) The method of the present invention is carried out, for example, as follows.
所要量の塩素系有機溶媒とアルカリ水溶液を反応器に仕
込み、攪拌下に加熱して還流させながらオルガノ錫ハラ
イドを滴下する。オルガノ錫ハライドの加水分解は常温
でも進行するが、常温では反応が遅く、且つ生成物の口
過性が悪いので実用的でない。還流下に反応を行なうこ
とは゛、反応温度を一定に保つことができるから有利で
ある。Required amounts of a chlorinated organic solvent and aqueous alkaline solution are charged into a reactor, and organotin halide is added dropwise while stirring and heating to reflux. Hydrolysis of organotin halides proceeds even at room temperature, but the reaction is slow and the product has poor oral properties at room temperature, so it is not practical. Carrying out the reaction under reflux is advantageous because the reaction temperature can be kept constant.
オルガノ錫ハライドは、必要に応じて塩素系有機溶媒に
溶解して滴下しても良い、オルガノ錫ハライドを滴下せ
ずに、その全量を塩素系有機溶媒とアルカリ水溶液との
中に一時に加えても良いが、この場合には急激な反応を
避けるために加熱は徐々に行うべきである。The organotin halide may be dissolved in a chlorinated organic solvent and added dropwise if necessary.The organotin halide may be added dropwise to the chlorinated organic solvent and the alkaline aqueous solution at once without dropping the organotin halide. However, in this case, heating should be done gradually to avoid a rapid reaction.
加水分解終了後、静置するとジオルガノ錫オキサイド〔
これはＲＳ ｎ （ＯＨ）２
ＲＳｎ （ＯＮａ） 、Ｒ２５ｎＯあるいはそれらの
オリゴマーの混合物として存在すると考えられる〕は、
塩素系有機溶媒層中に沈降析出する。After hydrolysis is complete, diorganotin oxide [
This is thought to exist as RS n (OH) 2 RS n (ONa), R25nO, or a mixture of these oligomers],
Precipitates in the chlorinated organic solvent layer.
上層の水層を分離し、新たに水を加えて攪拌洗浄し〔こ
の際、ＲＳ ｎ （ＯＮ ａ ） ２はＲ５ｎ（ＯＨ）
あるいはＲ２Ｓ ｎ Ｏに変化する、）、静置後に
水層を分離し、ジオルガノ錫オキサイドを塩素系有機溶
媒から日別する。この口過は極めて容易に行われる０日
別後、ジオルガノ錫オキサイドを乾燥すれば、極めて純
度の高いジオルガノ錫オキサイドを得ることができる。Separate the upper aqueous layer, add new water and wash with stirring [At this time, RS n (ON a ) 2 is R5n (OH)
Alternatively, it changes to R2S n O), after standing, the aqueous layer is separated and the diorganotin oxide is separated from the chlorinated organic solvent. This filtration process is extremely easy to carry out.If the diorganotin oxide is dried after 0 days, extremely pure diorganotin oxide can be obtained.
先豆立立」
上述したようにオルガノ錫ハライドの加水分解をベンゼ
ン、トルエン或いはキシレンなどのような疎水性芳香族
炭化水素系溶媒中で行なうと、生成物の口過性が極めて
悪いのであるが、加水分解を塩素系有機溶媒中で行なう
と、意外にもその生成物は口過の容易な粉末状で得られ
ることを木発明者らは見出したのである。この理由は詳
しくは不明であるが、おそらくこれら両系統の溶媒に対
する原料のオルガノ錫ハライド及び生成物のオルガノ錫
オキサイドの溶解度の影響があるものと考えられる。As mentioned above, when organotin halide is hydrolyzed in a hydrophobic aromatic hydrocarbon solvent such as benzene, toluene, or xylene, the product has extremely poor oral properties. The inventors of the present invention have surprisingly discovered that when hydrolysis is carried out in a chlorinated organic solvent, the product can be obtained in the form of a powder that is easily passed through the mouth. The reason for this is not clear in detail, but it is probably due to the influence of the solubility of the raw material organotin halide and the product organotin oxide in both of these solvents.
実−一施一一例
以下に実施例を挙げて本発明を更に具体的に説明するが
、本発明はこれによって何ら制限されるものではない。EXAMPLE 1 The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto in any way.
実施例１
内容積が１１の４頚フラスコに攪拌装置、温度計、還流
冷却器及び滴下ロートを付け、１２．５％の苛性ソーダ
水溶液５１７ｇと１．１．１−トリクロロエタン３３０
ｇを仕込んだ、攪拌下に加熱して還流下に滴下ロートか
らジーｎ−ブチル錫ジアイオダイドを主成分とするｎ−
ブチル錫アイオダイド混合物（ＣＨＳ ｎ Ｉ ３が
３ ％ 、（ＣＨ） Ｓ ｎ Ｉ ２が９２％、（Ｃ
４Ｈ９）３ＳｎＩが５％）２５０ｇをおよそ５０分間で
滴下した。滴下終了後、同温度で２時間攪拌を続けたの
ち、室温まで冷却した。静置すると、生成したジ−ｎ−
ブチル錫オキサイドは１．１．１−トリクロロエタン層
の下部に沈降した。上層のアルカリ水溶液層を除き、新
たに水３００ｍＪｌを注加し、ｌＯ分間攪拌後静置して
水層を除いた。有機溶媒層とジ−ｎ−ブチル錫オキサイ
ドスラリーとをヌッチェで吸引日別し、得られた細かい
白色結晶を１．１．１−）ジクロロエタン５０ｍＪＬで
洗浄後、水で充分に洗浄した。得られた白色結晶を８０
℃の送風乾燥機で８時間乾燥して、ジ−ｎ−ブチル錫オ
キサイドの粉末１１７ｇを得た。この粉末を分析した結
果、錫含量分析値は４７．７８％であり（計算値は４７
゜７５％）、ヨード分は計測できるほど存在していなか
った。Example 1 A 4-necked flask with an internal volume of 11 was equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, and 517 g of a 12.5% aqueous solution of caustic soda and 330 g of 1.1.1-trichloroethane were added.
n-butyltin diiodide as a main component was charged with di-n-butyltin diiodide from the dropping funnel after heating with stirring and refluxing.
Butyltin iodide mixture (CHS n I 3
3%, (CH) S n I 2 92%, (C
4H9) 250 g of 3SnI (5%) was added dropwise over approximately 50 minutes. After the dropwise addition was completed, stirring was continued for 2 hours at the same temperature, and then cooled to room temperature. When left standing, the generated G-n-
Butyltin oxide precipitated to the bottom of the 1.1.1-trichloroethane layer. The upper alkaline aqueous solution layer was removed, 300 mJl of water was newly added, and after stirring for 10 minutes, the mixture was allowed to stand and the aqueous layer was removed. The organic solvent layer and the di-n-butyltin oxide slurry were separated by suction using a Nutsche, and the obtained fine white crystals were washed with 50 mJL of 1.1.1-) dichloroethane and then thoroughly washed with water. 80% of the obtained white crystals
The mixture was dried for 8 hours in a blow dryer at .degree. C. to obtain 117 g of di-n-butyltin oxide powder. As a result of analyzing this powder, the tin content analysis value was 47.78% (the calculated value was 47.78%).
75%), and there was no measurable amount of iodine present.
口過母液の１．１．１−）ジクロロエタンと洗浄に用い
たｉ、ｔ、ｔ−トリクロロタンを合わせ、少量の水を分
液してから通常の操作で１．１．１−）ジクロロエタン
を留去すると、トリーｎ−ブチル錫オキサイドを主成分
とした残渣９．５ｇが得られた。ガスクロマトグラフ分
析の結果、この残渣はトリーｎ−ブチル錫オキサイドを
９４％含有することが分かった。Combine the 1.1.1-) dichloroethane of the filtration mother liquor and the i, t, t-trichlorothane used for washing, separate a small amount of water, and add 1.1.1-) dichloroethane using normal operations. After distillation, 9.5 g of a residue containing tri-n-butyltin oxide as a main component was obtained. Gas chromatographic analysis showed that the residue contained 94% tri-n-butyltin oxide.
実施例２
実施例１と同様な装置を用いて、２０％の苛性ソーダ水
溶液５０ｇと１，２−ジクロロプロパン１００ｇを仕込
み、攪拌下顎熱還流した。ジーｎ−オクチル錫ジアイオ
ダイド３５ｇと１゜２−ジクロロプロパン３０ｇの混合
液を滴下ロートから滴下した。滴下終了後、同温度で２
時間攪拌を続けたのち、実施例１と同様な操作を行なっ
て２０．５ｇのジーｎ−オクチル錫オキサイド粉末が得
られた。錫分析の結果、その含有量は３２．８０％であ
った。（計算値は３２．８８％である。）
実施例３
実施例１と同様な装置を用いて１２．５％の苛性ソーダ
水溶液５１７ｇと１．１．１−）ジクロロエタン２３２
ｇを仕込み、攪拌下に加熱還流した、ジ−ｎ−ブチル錫
ジクロライド１５０ｇと１．１．１−）ジクロロエタン
１００ｇの混合液を滴下ロートから滴下した０滴下終了
後に同温度で２時間攪拌を続けたのち、実施例１と同様
な操作を行なって、１２０ｇのジ−ｎ−ブチル錫オキサ
イド粉末が得られた０分析の結果、錫含有量は４７．７
５％であった。Example 2 Using the same apparatus as in Example 1, 50 g of a 20% aqueous solution of caustic soda and 100 g of 1,2-dichloropropane were charged, and the mixture was stirred and heated under reflux. A mixed solution of 35 g of di-n-octyltin diiodide and 30 g of 1°2-dichloropropane was added dropwise from the dropping funnel. After finishing dropping, 2 at the same temperature.
After stirring for a certain period of time, the same operation as in Example 1 was carried out to obtain 20.5 g of di-n-octyltin oxide powder. As a result of tin analysis, the content was 32.80%. (The calculated value is 32.88%.) Example 3 Using the same apparatus as in Example 1, 517 g of a 12.5% aqueous solution of caustic soda and 232 g of 1.1.1-) dichloroethane were prepared.
A mixed solution of 150 g of di-n-butyltin dichloride and 100 g of 1.1.1-) dichloroethane, which had been heated to reflux with stirring, was added dropwise from the dropping funnel. After the completion of the dropwise addition, stirring was continued at the same temperature for 2 hours. Afterwards, the same operation as in Example 1 was carried out to obtain 120g of di-n-butyltin oxide powder.As a result of analysis, the tin content was 47.7.
It was 5%.
実施例４
実施例１と同様な装置を用いて、１０％苛性ソーダ水溶
液４２０ｇとモノクロロベンゼン２００ｇを仕込み、攪
拌下に加熱還流した。ジフェニル錫ジクロライド１２０
ｇと１．２−ジクロロベンゼン１００ｇをあらかじめ混
合しておき１滴下ロートから滴下した０滴下終了後、同
温度で２時間攪拌を行ない、実施例１と同様な処理を行
ない、真空乾燥機を用いて乾燥し９７゜５ｇ（収率９６
．７％）のジフェニル錫オキサイドを得た。Example 4 Using the same apparatus as in Example 1, 420 g of a 10% aqueous sodium hydroxide solution and 200 g of monochlorobenzene were charged and heated to reflux with stirring. Diphenyltin dichloride 120
g and 100 g of 1,2-dichlorobenzene were mixed in advance and added dropwise from the dropping funnel. After the completion of the 0 drop addition, the mixture was stirred at the same temperature for 2 hours, and the same treatment as in Example 1 was carried out using a vacuum dryer. and dried to give 97.5 g (yield: 96
．． 7%) of diphenyltin oxide was obtained.
１１立１】
本発明によって得られるジオルガノ錫オキサイドの粉末
は、口過が容易であるばかりでなく、未反応のオルガノ
錫ハライド類及びＲ５ｎｘｑから生ずるオキサイド類を
ほとんど含まない純度の良好なものである。[11] The diorganotin oxide powder obtained by the present invention is not only easy to pass through the mouth, but also has good purity, containing almost no unreacted organotin halides and oxides generated from R5nxq. .
Claims (1)
ェニル基又はシクロヘキシル基を表わし、Ｘはハロゲン
原子を表わす。） で表わされるジオルガノ錫ジハライド又は該ジオルガノ
錫ジハライドと 一般式 Ｒ＿ｐＳｎＸ＿ｑ （式中Ｒ及びＸは上記と同じ意義を有し、ｐ及びｑはそ
れぞれ０、１、３又は４を表わし、しかもｐとｑとの和
は４である。） で表わされるオルガノ錫ハライドとの混合物を塩素系有
機溶媒中においてアルカリ金属水酸化物または水酸化ア
ンモニウムの水溶液によって加水分解することを特徴と
するジオルガノ錫オキサイドの製造法。[Claims] A diorganotin dihalide represented by the general formula R_2SnX_2 (wherein R represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a cyclohexyl group, and X represents a halogen atom) or Diorganotin dihalide and general formula R_pSnX_q (In the formula, R and X have the same meanings as above, p and q each represent 0, 1, 3, or 4, and the sum of p and q is 4.) 1. A method for producing diorganotin oxide, which comprises hydrolyzing a mixture with an organotin halide represented by the formula in a chlorinated organic solvent with an aqueous solution of an alkali metal hydroxide or ammonium hydroxide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60131646A JPH0676422B2 (en) | 1985-06-19 | 1985-06-19 | Method for producing diorganotin oxide |
| KR1019860004848A KR900005390B1 (en) | 1985-06-19 | 1986-06-18 | Preparation method of diorganotin oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60131646A JPH0676422B2 (en) | 1985-06-19 | 1985-06-19 | Method for producing diorganotin oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61291592A true JPS61291592A (en) | 1986-12-22 |
| JPH0676422B2 JPH0676422B2 (en) | 1994-09-28 |
Family
ID=15062920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60131646A Expired - Lifetime JPH0676422B2 (en) | 1985-06-19 | 1985-06-19 | Method for producing diorganotin oxide |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0676422B2 (en) |
| KR (1) | KR900005390B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0276889A (en) * | 1988-06-03 | 1990-03-16 | Yoshitomi Pharmaceut Ind Ltd | Separation and preparation of alkyltin oxide |
-
1985
- 1985-06-19 JP JP60131646A patent/JPH0676422B2/en not_active Expired - Lifetime
-
1986
- 1986-06-18 KR KR1019860004848A patent/KR900005390B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0276889A (en) * | 1988-06-03 | 1990-03-16 | Yoshitomi Pharmaceut Ind Ltd | Separation and preparation of alkyltin oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| KR900005390B1 (en) | 1990-07-28 |
| JPH0676422B2 (en) | 1994-09-28 |
| KR870000347A (en) | 1987-02-18 |
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